Motor fuel composition



United States Patent 3,303,007 MOTOR FUEL COMPOSITION Frederick L. Mueller, Arlington Heights, Ill., assignor, by

mesne assignments, to Union Oil Company of California, Los Angeles,.Calif., a corporation of California No Drawing. Filed Sept. 3, 1963, Ser. No. 306,337 5 Claims. (CI. 44-56) This invention relates toa motor fuel composition comprising a hydrocarbon mixture boiling in the gasoline boiling range and certain amounts of methanol and the dioleate salt of N-oleyl 1,3-propylenediamine, which motor fuelhas the property of reducing engine wear. More particularly, this invention relates to a gasoline composition containing about 5 to 100 lbs. of said methanol and said dioleate salt per 1000 barrels of said hydrocarbon mixture, wherein the weight ratio of methanol to fatty amine salt is greater thanl to 1. A feature of this invention is the discovery that about 15 lbs. of methanol. per 1000 barrels of gasoline and about 5 lbs. of dioleate salt of N-oleyl 1,3-propyle'nediamine per 1000 barrels of gasoline is more effective thaneither additive used alone. g

It is known in the prior art use the combination of methanol, a fatty acid amide of hydroxy ethylenediamine and a small percent of an oil soluble ammonium sulphonate for the purpose of preventing the accumulation of Water in the. fuelsystem and also preventing rust in the engine. In some prior art compositions, methanol is added as a de-icer and various amides and sulphonates are added for theinemulsifying effect. In these compositions, the combination of the amide and sulphonate is necessary.to obtainthe' desired emulsification and there is no indication that the compositions reduce wear in the engine. Other prior art compositions are known which contain commercial alcohol, aliphatic amine, benzyl amine, piperidine amine, fatty acid amine salts and organic phosphates. In the latter instance, the phosphates are the antiwear agents.

Accordingly, it is a primary object of this invention to provide a mot-or fuel comprising a hydrocarbon mixture boiling in the gasoline boiling range containing antiwear amounts of methanol and dioleate salt of N-oleyl 1,3- propylenediamine.

Another object of this invention is to provide improved fuel compositions for use in spark-ignition, internal combustion engines, consisting essentially of gasoline and a minor portion of from about 5 to 100 lbs. methanol and the dioleate salt of N-oleyl 1,3-propylenediamine per 1000 barrels of gasoline wherein said methanol and fatty amine salt are present in weight ratios of about 1 to 8 parts of methanol per part of said fatty amine salt.

These and other objects of the invention will become apparent or described as the description thereof proceeds.

In order to demonstrate the invention the following experimental data is presented. I

A single-cylinder COT engine was equipped with a radioactive piston ring. The engine was run a total of about 100 hours on several different gasoline compositions and the wear rate was determined by measuring radiation given off by radioactive particles worn 0d the piston ring and carried by the lubricating oil for the engine. The gasoline used in these tests had the following characteristics:

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TABLE 1 Gravity, API 57.5 Reid vapor pressure, p.s.i 6.1 ASTM distillation:

IBP F 100 10% F 156 50% F 223 90% F 334 EP F 426 Residue percent 1.2 3 Loss do 0.4 TEL 'ml./gal 3.15 Sulfur percent 0.053 Hydrocarbon analysis:

Saturates "percent" 56 Olefins do 17 Aromatics do 27 Each test was conducted first without an additive of any kind and then with the experimental additive or additive combination, and any change in wear rate was noted. The results are given in Table '11 below:

TABLE II Additive-Concentrations expressed as lbs/1,000 barrels Results Example Duomeen 0 Additive Wear Percent Dioleate Methanol A" (mg/hr.) Decrease in wear 0. 25 0. 1G 36 0.19 24 -0. 40 0. 50 -25 0. 2G 0. 26 0 0. 66 0. 45 32 0. 35 0. 31 ll 0. 54 0. 58 7 Additive A is a gasoline antiwear additive used for comparison.

The var10us Duomeens are products of Armour Chemical Division and have the formula l RNCH2-CH2CI-IzNHz wherein R is derived from various fatty acids and is aliphatic, having 8 to 30 carbon atoms.- By reaction of the Duomeens with fatty acids the monoand disalts are obtained. Thus the dioleate salt of N-oleyl 1,3- propylenediamine is the reaction product of 2 moles of oleic acid and 1 mole of N-oleyl 1,3-propylene diamine.

The methanol used may be technical or CF. grade methanol. The methanol and dioleate salt are blended in any order and in compounding the gasoline compositions of this invention any of the known blending procedures can be used for incorporating the ingredients therein. The antiwear advantages of the additive combination of this invention can be obtained with any motor fuel comprising combustible hydrocarbons boiling in the gasoline boiling range. The gasoline may comprise a single hydrocarbon or a mixture of hydrocarbons qualifying as a motor fuel or as straight-run gasoline or gasoline obtained from a conventional cracking process, or mixtures thereof. The base gasoline may also contain components obtained from various other refinery processes, such as alkylation, isomerization, hydr ogenation, polymerization, catalytic reforming hydroforming, dehydroforming, dehydrogenation, hydroisomerization, hydrodisulfurization, polyforming, Platforming or combinations of two or more of such processes, as well as synthetic gasolines obtained by the Fischer-Tropsch and related processes.

Modern gasolines will contain varying proportions of parafiins. olefins, naphthenes and aromatics and generally will boil in the range of about 100 to 425 F. The aromatic components may be present in amounts varying from 10 to 90%. The paraffin constituents may vary from 5 to 35% and the naphthenes from 0 to 15%. A typical blend of naphtha reformate may contain 25% paraifins, 3% naphthenes and 72% aromatics or 35% parafiins, 15% olefins, 7% naphthenes and 44% aromatics. Blends of butane, mixed xylenes, alkylates, and light FCC gasoline can be used.

The gasoline blend may qualify as a regular or premium gasoline. A typical premium gasoline, as used to illustrates this invention, besides a small amount of lower-alkyl lead compound as an anti-knick agent, may also contain small amounts of non-hydrocarbon substances or addition agents to impart various properties thereto for use in internal combustion engines, e.'g., scavengers, corrosion inhibitors, oxidation inhibitors, de hazing agents, anti-rustadditives, dyes, etc. Such gasolines have research method octane numbers of about 90 to 105 and motor method octane numbers of about 80- 98.

Tetra-lower-alkyl lead compounds are most widely known anti-knock agents and tetraethyl lead is most commonly used for this purpose. TEL Motor Mix is used in commercial practice to add tetraethyl lead and scavenger combinations to gasoline. fMotor Mix contains 59.2% tetraethyl lead, 13.0% ethylene dibromide,-

23.9% ethylene dichloride and 3.9% hydrocarbon diluent, dyes, etc. The tetra-lower-alkyl lead compound with scavengers is used in an amount to provide about 1.0 theory of ethylene dichloride and 0.5 theory of ethylene hromi u qry ds t nath tqi hiqme r q m trsquired for reaction with the lead content of the tetraalkyl lead. The gasoline composition used in accordance with this invention can contain 1 to 4 grams of lead as lead alkyl per gallon of gasoline.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A motor fuel composition consisting essentially of a hydrocarbon mixture boiling in the gasoline boiling range and about 5 to lbs. of methanol and the dioleate salt of N-oleyl 1,3-propylene diamine per 1000 barrels of said hydrocarbon mixture, the weight ratio of said methanol to dioleate salt being greater than 1 to l. 2. A motor fuel composition in accordance with claim 1 in which the weight ratio of said methanol to dioleate salt is about 3 to 1. v I

3. A motor fuel composition in accordance with claim 2 in which about 15 lbs. of methanol and about 5 lbs. of said dioleate salt are present per 1000 barrels of said hydrocarbon mixture. I

4. Ajmotor fuel composition consisting essentially of a gasoline boiling in the range of about 100 to 425 F. containing about 15 lbs. of methanol and about 5 lbs. of the dioleate salt of N-0ley1-1,3-propylene diamine per 1000 barrels of said gasoline. I I v 5. A motor fuel composition consisting essentially of a gasoline boiling in the range of about 100 to 425 F. containing about 1 to 4 grams of lead as lead alkyl per gallon of said gasoline and containing about 15 lbs. of methanol and about 5 lbs. of the 'dioleate salt of N-oleyl- 1,3-propylene diamine per 1000 barrels of said gasoline.

References. Cited by the Examiner UNITED STATES PATENTS 2,736,658 2/1956 Pfohl'etal. 4472 X 2,776,194 1/1957 Scheumann '44--56 2,798,045 7/ 1957 Buck et a1. 25234 3,084,034 4/ 1963 Kalinowski 4466 DANIEL E. WYMAN, Primary Examiner.

W. J. SHINE, Assisiant Examiner. 

1. A MOTOR FUEL COMPOSITION CONSISTING ESSENTIALLY OF A HYDROCARBON MIXTURE BOILING IN THE GASOLINE BOILING RANGE AND ABOUT 5 TO 100 LBS. OF METHANOL AND THE DIOLEATE SALT OF N-OLEYL 1,3-PROPYLENE DIAMINE PER 1000 BARRELS OF SAID HYDROCARBON MIXTURE, THE WEIGHT RATIO OF SAID METHANOL TO DIOLEATE SALT BEING GREATER THAN 1 TO
 1. 